Rhodolalkyletherester.



i NITED STATES PATENT OFFICE.

ALBRECHT SCHMIDT, OF HCCHST-ON-THE-MAIN, GERMANY, ASSIGNOR TO THEFARBWERKE, VORMALS MEISTER, LUCIUS & BRHNING, OF SAME PLACE.

RHODOLALKYLETHERESTER.

SPECIFICATION forming part of Letters Patent No.656,426, dated August21, 1900. Application filed December 6, I899. $erial No. 739,370.($pecimens.)

To all whom it may concern:

Be it known that I, ALBRECHT SCHMIDT,

Ph. D. a citizen of the Empire of Germany, re-

siding at Hochst-on-the-Main, Germany, have invented certain new anduseful Improvements in the Process for Manufacturing Dyestuifs Fast toSoap from the Rhodol Series, of which the following is a specification.

The rhodols of the type are inapplicable as dyestuffs on account oftheir not being fast to soap; also, the rhodol-carboxylicesters obtainedby esterification at the carboxylic group and described in the GermanPatent No. 96,108 and German application No. B. 20,717 are exceedinglyfugitive to soap. I have found that this lack of fastness has solely tobe traced back to the free hydroxyl group and that the dyestuffsobtained on substituting the hydroxyl hydrogen by an alkyl group,(methyl, ethyl, benzyl, &c.,) of the type cation.

in contrast to the dyestuffs of the type I N/HY\I/\/\I/(OHI') l I lyield shades exceedingly fast to soap on calico mordanted with tannin.Substances of this kind have hitherto not been known. They are obtainedby alkaline or neutral alkylation of the rhodols orrhodol-carboxylicesters.

They may also of course be obtained by es- 7o terification of thehitherto-unknown rhodolhydroxyl-ethersi c'c'c' kali, as is the case withthe rhodolcarboxylicesters; but alkylated rhodols alkylated at thehydroxyl group, which are soluble in acids, but not in alkalies, andwhich in their behavior are quite similar to rhod'amines, as alkylatingagents-mayserve those usually employed for the manufacture ofphenolethers-such, for instance, as ethylbromiid, benzylchlorid,dialkylsulfate, (dimethylsulfate.) According as one starts from rhodolsor from the rhodolcarboxylicesters or even from rhodolhydroxylicethersrhodoletheresters may be produced in this way with similar or differentalkyl groups.

I. Resorcz'nol diethyl rhodol metlz yl'ethermethylester:

O CmwmmW OQH l l v l weight, of thehydrochloride of diethyl-rhol dol andone hundred and twenty parts of soda-ash, are treated with one hundredand ninety parts of-dimethylsulfate.

about 85 solid. time at ordinary temperature and is again heated foranother one-half hour to 90 centigrade. The pulverized mass is stirredwith hydrochloric acid diluted with water till it is completelydissolved and then salted out, whereupon the dyestuff is precipitated asa semiliquid red-yellow oil, gradually solidifying to crystallinecrusts. The dyestufi is readily soluble in water and also in a nottooconcentrated solution of common salt. It is not precipitated by asolution of sodium carbonate. When boiled with sodium carboate or whentreating the solution with sodalye, hydrolysis takes. place, whereuponthe diethylqrhodolhydroxyl. methylether sepas rates as: a colorlessloose powder. ethylrhodolmethylether mcthylester dyes calico treatedwith tannin in ardent yellow-w redg shades. fast to soap.

' From d z'ethg Z-rhoclolcarboasylicesten- Aethorough, mixture offorty-one parts, by weight, of diethyl-rhodolcarboxylicesten (ac cordingto No. B. 20,717)v and twentyrparts, by-weight,,of soda-ash are treatedwith thirty parts, by weigh-t, of dimethylsulfate and1fu. r

ample I (a). also identical with that described in example I (or).droxyl-methylether with dimethylsulfate it Whilestirj ring, the massbecomes heated y itself to III. Resoromol dtmethyl rhodol methy lethercentigrade, viscuous and finally 1 I It is then allowed to stand forsome ethyl compounds is to be mentioned;

The. di-

ther operated with exactly as in example I (a). The dyestuff thusobtained is identical with that described in example I (a).

(c) From diethg l-rhodoZ-hydroxyZ-methylether.Thirty-eight parts, byweight, of diethyl-rhodol-hydroxyl-methylether are heated for some timeto to centigrade, preferably with some soda-ash, and twenty-five parts,by weight, of dimethylsulfate. The mass is further worked as describedin ex- The dyestufi thus obtained is Instead of treatingdiethyl-rhodol-hymay also be esterified with methyl-alcohol and amineral acid.

II. Resorcinol diethyl rhoclol mehyletherethylester.

methg Zester. The procedureis the same as. described in example I (a),(b),and- (o), No characteristic. distinct-ionf from the; correspondingdi- The methyl compound, however, dyes somewhat more ardentl y: Itshydrochloratexis'yet morereadilysol-uble than that of the diethyl com.-

pound.

IN. Resoreinol-diethyZ-rhodol-benzg Zethermethylestcr.

Eighty-four parts,by weight, of the hydrochloride of diethyl-rhodol aredissolved in two hundred parts, by weight, of water and seventy parts,by Weight, of soda-lye of 40 Baum, specific gravity, and this solution,While adding fifty parts, by weight, of benzylehlorid, is boiled forseveral hours in a vessel provided with an inverted condenser, when thediethyl-rhodol-benzylether, insoluble in alkali,

M/ $300 a L j separates. When dried and pulverized, it is mixed Withdimethylsulfate (one part) and heated, preferably with soda-ash,(one-half part,) for about one and one-half hours from to centigrade.The pulverized mass is stirred with hydrochloric acid, and Water isadded till it dissolves. The solution is then filtered and salted out.The'hydrochlorate gradually solidifies to a brittle mass. It is readilysoluble in water. A solution of sodium carbonate does not precipitateit. Sodalye produces hydrolysis, whereupon thediethyl-rhodol-benzylether separates as a resinous body. The vividyellow-red shades produced on calico treated with tannin are hardly tobe distinguished from those of the correspondin grhethylethenmethylester.

V. Resorcrlnol-m0n0-eihyZ-rhod0lm6thyletherm at hylesier,

r ooocn,

chlorate, readily soluble in Water, dyes yellower than the correspondingethyl compound. The solutions incontrast to the latter are of a strongyellow fluorescence.

VI. (Hydrochinon) diethyl rhodol methyl eiher-meihg Zestcr.

Y I l the corresponding hydrochinon rhodolme thylether-nlethylester isobtained in exactly the same manner and of analogous properties, yetwith this difference that the shades obtained therewith on calicotreated with tannin are not yellowred,but blue-red. These shades arealso fast to soap.

VII. (Diowynaphthalcne)diethyl-rhodoZ-meth'ylether'mcthylester.

l I I The diethyl-rhodol obtained from 2. '7 dioxy naphthalene anddiethyl-ln aniidooxy-benzoylbenzoic acid having the probableconstitution yields when treated according to example I (ct) and (c) amethylether-methylester quite 4 etAz analogous to the previous ones, andwhich is strictly distinguished from the carboXyl-icmethylester obtainedfrom this rhodol by means of esterification with methyl alcohol and anacid. The solutions of the carboxylicmethylester are precipitated bysodium carbonate, but the former not. The bluish-red tints obtained oncalico treated with tannin of the shade 6G are fast to soap in the firstcase and not in the latter.

Having now described my invention, what I claim is As new products, therhodolalkyletheres- ALBRECHT SCHMIDT.

Witnesses HEINRICH HAHN, ALFRED BRISBOIS.

